JPWO2014073536A1 - Polyvalent phenylene ether novolak resin, epoxy resin composition and cured product thereof - Google Patents
Polyvalent phenylene ether novolak resin, epoxy resin composition and cured product thereof Download PDFInfo
- Publication number
- JPWO2014073536A1 JPWO2014073536A1 JP2014545711A JP2014545711A JPWO2014073536A1 JP WO2014073536 A1 JPWO2014073536 A1 JP WO2014073536A1 JP 2014545711 A JP2014545711 A JP 2014545711A JP 2014545711 A JP2014545711 A JP 2014545711A JP WO2014073536 A1 JPWO2014073536 A1 JP WO2014073536A1
- Authority
- JP
- Japan
- Prior art keywords
- phenylene ether
- resin
- resin composition
- epoxy resin
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920005989 resin Polymers 0.000 title claims abstract description 110
- 239000011347 resin Substances 0.000 title claims abstract description 110
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229920003986 novolac Polymers 0.000 title claims abstract description 55
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 46
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 125000000962 organic group Chemical group 0.000 claims abstract description 6
- 239000004793 Polystyrene Substances 0.000 claims abstract description 4
- 229920002223 polystyrene Polymers 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 13
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 150000002989 phenols Chemical class 0.000 claims description 8
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 4
- -1 for example Chemical class 0.000 description 37
- 239000011342 resin composition Substances 0.000 description 32
- 239000003795 chemical substances by application Substances 0.000 description 31
- 239000002904 solvent Substances 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 229920001955 polyphenylene ether Polymers 0.000 description 17
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 239000011574 phosphorus Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- 125000005647 linker group Chemical group 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 235000010290 biphenyl Nutrition 0.000 description 7
- 239000004305 biphenyl Substances 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000002966 varnish Substances 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- IYJMFNNRVITCDG-UHFFFAOYSA-N biphenylene;phenol Chemical group OC1=CC=CC=C1.C1=CC=C2C3=CC=CC=C3C2=C1 IYJMFNNRVITCDG-UHFFFAOYSA-N 0.000 description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 5
- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical class C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 4
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000006839 xylylene group Chemical group 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 229910000064 phosphane Inorganic materials 0.000 description 3
- 150000003002 phosphanes Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001226 reprecipitation Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 2
- YGYPMFPGZQPETF-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C=2C=C(C)C(O)=C(C)C=2)=C1 YGYPMFPGZQPETF-UHFFFAOYSA-N 0.000 description 2
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 2
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 2
- CIRRFAQIWQFQSS-UHFFFAOYSA-N 6-ethyl-o-cresol Chemical compound CCC1=CC=CC(C)=C1O CIRRFAQIWQFQSS-UHFFFAOYSA-N 0.000 description 2
- IXCOKTMGCRJMDR-UHFFFAOYSA-N 9h-fluorene;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=C2CC3=CC=CC=C3C2=C1 IXCOKTMGCRJMDR-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
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- PFJGMUWBVMNSSU-UHFFFAOYSA-N [2-(hydroxymethyl)-3-phenylphenyl]methanol Chemical compound OCC1=CC=CC(C=2C=CC=CC=2)=C1CO PFJGMUWBVMNSSU-UHFFFAOYSA-N 0.000 description 2
- AMNPXXIGUOKIPP-UHFFFAOYSA-N [4-(carbamothioylamino)phenyl]thiourea Chemical compound NC(=S)NC1=CC=C(NC(N)=S)C=C1 AMNPXXIGUOKIPP-UHFFFAOYSA-N 0.000 description 2
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
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- 150000004780 naphthols Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
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- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
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- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
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- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- SXXILWLQSQDLDL-UHFFFAOYSA-N bis(8-methylnonyl) phenyl phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OC1=CC=CC=C1 SXXILWLQSQDLDL-UHFFFAOYSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical group C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- RKMJXTWHATWGNX-UHFFFAOYSA-N decyltrimethylammonium ion Chemical class CCCCCCCCCC[N+](C)(C)C RKMJXTWHATWGNX-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- NOCMYCSJUZYBNE-UHFFFAOYSA-N dioctadecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(O)OCCCCCCCCCCCCCCCCCC NOCMYCSJUZYBNE-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- GQKZBCPTCWJTAS-UHFFFAOYSA-N methoxymethylbenzene Chemical compound COCC1=CC=CC=C1 GQKZBCPTCWJTAS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- FDAKZQLBIFPGSV-UHFFFAOYSA-N n-butyl-2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CCCCNC1CC(C)(C)NC(C)(C)C1 FDAKZQLBIFPGSV-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- FZCZZWSFIAHGAD-UHFFFAOYSA-N octadecyl 3-[3-tert-butyl-4-[[2-tert-butyl-6-methyl-4-(3-octadecoxy-3-oxopropyl)phenoxy]-hydroxyphosphanyl]oxy-5-methylphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OCCCCCCCCCCCCCCCCCC)=CC(C)=C1OP(O)OC1=C(C)C=C(CCC(=O)OCCCCCCCCCCCCCCCCCC)C=C1C(C)(C)C FZCZZWSFIAHGAD-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical class CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
Abstract
本発明は、耐熱性が高く、誘電特性に優れる硬化物を与える多価フェニレンエーテルノボラック樹脂、およびそれを含むエポキシ樹脂組成物を提供することを目的とする。本発明の多価フェニレンエーテルノボラック樹脂は、分子量400〜8000(重量平均分子量 ポリスチレン換算)のポリ(フェニレンエーテル)樹脂が有機基により連結されている。An object of the present invention is to provide a polyvalent phenylene ether novolak resin which gives a cured product having high heat resistance and excellent dielectric properties, and an epoxy resin composition containing the same. In the polyvalent phenylene ether novolak resin of the present invention, poly (phenylene ether) resins having a molecular weight of 400 to 8000 (weight average molecular weight in terms of polystyrene) are linked by an organic group.
Description
本発明は耐熱性、電気特性(誘電特性等)が要求される電気電子材料用途に好適なノボラック樹脂、エポキシ樹脂組成物、およびその硬化物に関する。 The present invention relates to a novolac resin, an epoxy resin composition, and a cured product thereof suitable for use in electrical and electronic materials that require heat resistance and electrical properties (dielectric properties, etc.).
エポキシ樹脂組成物は作業性及びその硬化物の優れた電気特性、耐熱性、接着性、耐湿性(耐水性)等により電気・電子部品、構造用材料、接着剤、塗料等の分野で幅広く用いられている。 Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.
しかし近年、電気・電子分野においてはその発展に伴い、樹脂組成物の高純度化をはじめ耐湿性、密着性、誘電特性、フィラー(無機または有機充填剤)を高充填させるための低粘度化、成型サイクルを短くするための反応性のアップ等の諸特性の一層の向上が求められている。又、構造材としては航空宇宙材料、レジャー・スポーツ器具用途などにおいて軽量で機械物性の優れた材料が求められている。 However, in recent years, with the development in the electric / electronic field, moisture resistance, adhesion, dielectric properties, low viscosity for high filling of filler (inorganic or organic filler) as well as high purity of resin composition, There is a need for further improvements in various properties such as increased reactivity to shorten the molding cycle. Further, as a structural material, there is a demand for a material that is lightweight and has excellent mechanical properties in applications such as aerospace materials and leisure / sports equipment.
半導体封止分野、基板(基板自体、もしくはその周辺材料)においては、その半導体の変遷に従い、薄層化、スタック化、システム化、三次元化と複雑になっていき、非常に高いレベルの耐熱性や高流動性といった要求特性が求められる。さらには高速通信を実現するために半導体周辺材料には優れた誘電特性が求められる。この誘電特性が悪いと電気信号の遅延・ノイズの発生により、電気信号の高速化が困難となる。
このような分野において、特にサーバー等のネットワーク基板においては高周波における誘電特性が求められる。年々進化し続けるネットワーク環境には、誘電特性の中でも特に低誘電正接が重要となる。このような用途には主にポリ(フェニレンエーテル)樹脂が用いられることが多く、さまざまな検討がなされている。
ポリ(フェニレンエーテル)樹脂はその非常に優れた誘電特性が特徴であるが、その誘電特性を体現するため、官能基が極めて少なく、その耐熱性の低さが課題となっている。
近年の報告によればこういった課題に対し、官能基を入れる等の手法(a)や、2官能にする(b)といったような検討がなされているが、(a)では官能基の導入が困難なことからほとんど実用化されておらず、(b)では多少の改善はあるが、未だ足りないレベルである。
こういった課題に直面し、我々は本発明に至った。
即ち、本発明は、優れた誘電特性を維持しながら、耐熱性に優れる硬化物を与えることができる多価フェニレンエーテルノボラック樹脂、これを含有するエポキシ樹脂組成物、およびその硬化物を提供することを目的とする。In the field of semiconductor encapsulation and substrates (substrate itself or its peripheral materials), as the semiconductor transitions, it becomes complicated with thinning, stacking, systemization, and three-dimensionalization, and a very high level of heat resistance. Required characteristics such as stability and high fluidity are required. Furthermore, in order to realize high-speed communication, semiconductor peripheral materials are required to have excellent dielectric properties. If this dielectric property is poor, it is difficult to increase the speed of the electric signal due to delay of the electric signal and generation of noise.
In such a field, particularly in a network substrate such as a server, dielectric properties at high frequencies are required. In a network environment that continues to evolve year by year, low dielectric loss tangent is particularly important among dielectric properties. For such applications, poly (phenylene ether) resins are often used, and various studies have been made.
Poly (phenylene ether) resin is characterized by its very excellent dielectric properties, but in order to embody the dielectric properties, there are very few functional groups and its low heat resistance is a problem.
According to recent reports, studies such as adding a functional group (a) and bifunctional (b) have been made to deal with these problems. However, in (b), there is a slight improvement, but it is still insufficient.
In the face of these challenges, we have arrived at the present invention.
That is, the present invention provides a polyvalent phenylene ether novolak resin capable of giving a cured product having excellent heat resistance while maintaining excellent dielectric properties, an epoxy resin composition containing the same, and a cured product thereof. With the goal.
本発明者らは前記したような実状に鑑み、鋭意検討した結果、本発明を完成させるに至った。
すなわち本発明はAs a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention
(1)
分子量400〜8000(重量平均分子量 ポリスチレン換算)のポリ(フェニレンエーテル)樹脂を有機基により連結された多価フェニレンエーテルノボラック樹脂、(1)
A polyvalent phenylene ether novolak resin in which poly (phenylene ether) resin having a molecular weight of 400 to 8000 (weight average molecular weight in terms of polystyrene) is linked by an organic group,
(2)
有機基が下記式(1)の少なくともいずれかで表される(1)に記載の多価フェニレンノボラック樹脂、(2)
The polyvalent phenylene novolak resin according to (1), wherein the organic group is represented by at least one of the following formula (1):
(式中、*部はポリ(フェニレンエーテル)樹脂のベンゼン骨格に結合する。) (In the formula, the * part is bonded to the benzene skeleton of the poly (phenylene ether) resin.)
(3)
(1)または(2)記載のポリ(フェニレンエーテル)樹脂が、ビフェノール類またはビスフェノール類と、フェノール化合物類の酸化重合体である(1)または(2)記載の多価フェニレンエーテルノボラック樹脂、(3)
The poly (phenylene ether) resin described in (1) or (2) is an oxidized polymer of biphenols or bisphenols and phenol compounds, (1) or a polyvalent phenylene ether novolak resin described in (2),
(4)
前項(1)〜(3)のいずれか1項に記載の多価フェニレンエーテルノボラック樹脂を少なくとも1種含有するエポキシ樹脂組成物、
(5)
前項(4)に記載のエポキシ樹脂組成物を硬化させて得られる硬化物、
を、提供するものである。(4)
An epoxy resin composition containing at least one polyphenylene ether novolak resin according to any one of (1) to (3) above;
(5)
A cured product obtained by curing the epoxy resin composition according to item (4),
Is provided.
本発明の多価フェニレンエーテルノボラック樹脂を使用するエポキシ樹脂組成物の硬化物は、高度な誘電特性を有するだけでなく、優れた耐熱性を発現し、電気電子部品用絶縁材料及び積層板(プリント配線板、ビルドアップ基板など)やCFRPを始めとする各種複合材料、接着剤、塗料等に有用である。特に半導体素子を保護する半導体封止材料にきわめて有用である。 The cured product of the epoxy resin composition using the polyphenylene ether novolak resin of the present invention has not only high dielectric properties but also excellent heat resistance, and an insulating material for electrical and electronic parts and a laminate (print Wiring board, build-up board, etc.) and various composite materials including CFRP, adhesives, paints, etc. In particular, it is extremely useful for a semiconductor sealing material for protecting a semiconductor element.
本発明の多価フェニレンエーテルノボラック樹脂はポリ(フェニレンエーテル)構造の樹脂がアルキレン基等の有機基(以下、結合基又は連結基とも称する)を介して結合した構造を有する。すなわち、本発明の多価フェニレンエーテルノボラック樹脂は、ポリ(フェニレンエーテル)構造の樹脂とノボラック樹脂の構造を有する樹脂である。 The polyvalent phenylene ether novolak resin of the present invention has a structure in which a resin having a poly (phenylene ether) structure is bonded through an organic group such as an alkylene group (hereinafter also referred to as a linking group or a linking group). That is, the polyvalent phenylene ether novolak resin of the present invention is a resin having a poly (phenylene ether) structure resin and a novolac resin structure.
ポリ(フェニレンエーテル)構造の樹脂とは具体的には前述の特許文献1、特許文献2に記載の樹脂であり、キシレノールやトリメチルフェノールの酸化重合体が一般的であるが、特許文献2に記載の樹脂のようにビフェノール類や、ビスフェノール類と2,6−キシレノール等のフェノール化合物類の酸化重合体等もあげることができる。
ここで、ビスフェノール類としては、例えば、ビスフェノールA、ビスフェノールF、ビスフェノールS、ビスフェールIといったビスフェノール類を使用することができる。市販品としてはSABIC製のPPO(登録商標)が挙げられ、特に分子量の範囲からSA120やSA90−100等が好ましい。また、特に多官能化の度合いからSA90−100のような2官能のものを使用することが好ましい。ビフェノール類としては、例えば、下記式の化合物が挙げられる。Specifically, the resin having a poly (phenylene ether) structure is a resin described in Patent Document 1 or Patent Document 2 described above, and an oxidized polymer of xylenol or trimethylphenol is generally used. Examples thereof include biphenols and oxidized polymers of phenol compounds such as bisphenols and 2,6-xylenol.
Here, as the bisphenols, for example, bisphenols such as bisphenol A, bisphenol F, bisphenol S, and bisphenol I can be used. Examples of commercially available products include PPO (registered trademark) manufactured by SABIC, and SA120 and SA90-100 are particularly preferred from the range of molecular weight. In particular, it is preferable to use a bifunctional compound such as SA90-100 from the degree of polyfunctionalization. Examples of the biphenols include compounds represented by the following formula.
(式中、R1は各々独立の置換基を表し、水素原子、ハロゲン原子、炭素数1〜3のアルキル基、アラルキル基、アリール基、アルコキシ基であり、tは1〜4の整数を示す。)(In the formula, each R 1 represents an independent substituent, which is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an aralkyl group, an aryl group, or an alkoxy group, and t represents an integer of 1 to 4. .)
フェノール化合物類としては、o−クレゾール、2,6−ジメチルフェノール、2,3,6−トリメチルフェノール、2−エチルフェノール、2−メチル−6−エチルフェノール、2,6−ジエチルフェノール、2−n−プロピルフェノール、2−エチル−6−n−プロピルフェノール、2−メチル−6−クロルフェノール、2−メチル−6−ブロモフェノール、2−メチル−6−イソプロピルフェノール、2−メチル−6−n−プロピルフェノール、2−エチル−6−ブロモフェノール、2−メチル−6−n−ブチルフェノール、2,6−ジ−n−プロピルフェノール、2−エチル−6−クロルフェノール、2−メチル−6−フェニルフェノール、2−フェニルフェノール、2,6−ジフェニルフェノール、2,6−ビス−(4−フルオロフェニル)フェノール、2−メチル−6−トリルフェノール、2,6−ジトリルフェノール等の一価フェノール化合物が挙げられる。 As phenol compounds, o-cresol, 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-n -Propylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6-n- Propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol 2-phenylphenol, 2,6-diphenylphenol, 2,6-bis- (4-fluoro Eniru) phenol, 2-methyl-6-tolyl phenols, monohydric phenolic compounds such as 2,6-di-tolyl phenols.
使用するポリ(フェニレンエーテル)樹脂の分子量としては、400〜8000(重量平均分子量 ゲルパーミエーションクロマトグラフィー ポリスチレン換算)であり、好ましくは500〜4000である。
使用する樹脂の分子量が高すぎる場合、溶剤への相溶性や、他の樹脂との相溶性で支障をきたし、硬化物に取り込む際に分離し、硬化不良、特性の偏在化をもたらすことから好ましくない。また分子量が小さい場合、特に200程度の場合、一般的なノボラック樹脂と比べ大きな誘電特性の差が出せず、好ましくない。
これら分子量の制御としては単純に分子をつなげるだけでなく、ラジカルによる解重合により分子量制御が可能となった事例も挙げられる。The molecular weight of the poly (phenylene ether) resin to be used is 400 to 8000 (weight average molecular weight, gel permeation chromatography, converted to polystyrene), and preferably 500 to 4000.
If the molecular weight of the resin used is too high, it may cause problems with compatibility with solvents and compatibility with other resins, and may be separated when incorporated into a cured product, resulting in poor curing and uneven distribution of characteristics. Absent. Further, when the molecular weight is small, particularly about 200, it is not preferable because a large difference in dielectric characteristics cannot be obtained as compared with a general novolac resin.
Examples of the control of these molecular weights include not only simply connecting molecules but also examples in which molecular weight control is possible by depolymerization with radicals.
本発明の多価フェニレンエーテルノボラック樹脂は、フェニレン構造を結合基で繋げることでノボラックもしくはそれに類する形(便宜上、すべてノボラックと表現する)となる。
結合基としては炭素数1〜20の炭化水素基であることが好ましい。具体的にはメチレン、エチレン、プロピレン、シクロヘキサン-ジイル、フェニルメチレン、フェニレンビスメチレン、ビエニレンビスメチレン、フェニレンビスエチレン、フェニレンビスプロピレン、等が挙げられる。
本発明における結合基としては、特に下記式(1)に示す構造が好ましい。The polyvalent phenylene ether novolak resin of the present invention becomes a novolak or a similar form (all expressed as a novolak for convenience) by connecting the phenylene structure with a bonding group.
The linking group is preferably a hydrocarbon group having 1 to 20 carbon atoms. Specific examples include methylene, ethylene, propylene, cyclohexane-diyl, phenylmethylene, phenylene bismethylene, bienylene bismethylene, phenylene bisethylene, phenylene bispropylene, and the like.
As the bonding group in the present invention, a structure represented by the following formula (1) is particularly preferable.
(式中、*部はポリ(フェニレンエーテル)樹脂のベンゼン骨格に結合する。) (In the formula, the * part is bonded to the benzene skeleton of the poly (phenylene ether) resin.)
これら連結基の結合方法としては、原料ポリ(フェニレンエーテル)樹脂と各種アルデヒド類、ケトン類、ベンジルメチレン化合物、ビニルベンゼン構造を有する化合物等の結合形成化合物を利用して、溶剤存在下、酸性または塩基性条件下で加熱することで合成できる。 As a method for bonding these linking groups, a raw material poly (phenylene ether) resin and various aldehydes, ketones, benzylmethylene compounds, bond-forming compounds such as compounds having a vinylbenzene structure, etc. are used in the presence of a solvent. It can be synthesized by heating under basic conditions.
ここで、結合形成化合物の具体的な例としては、ホルムアルデヒド、アセトアルデヒド、グリオキザール、プロピルアルデヒド、イソバレルアルデヒド、オクチルアルデヒド、フルフラール、ベンズアルデヒド、ピリジンカルボアルデヒド等のアルデヒド類、アセトン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン等のケトン類、キシリレングリコール、キシリレンジハライド(ハロゲン:塩素、臭素などが挙げられる。)、ビスアルコキシメチルベンゼン(キシリレンビスアルキルエーテル、具体的にはビスメトキシメチルベンゼン、ビスエトキシメチルベンゼン、ビスプロポキシメチルベンゼン、ビスブトキシメチルベンゼン、ビスフェノキシメチルベンゼン、ビスアリルオキシメチルベンゼンなど、炭素数1〜6のアルコキシメチル体など。本合成反応においては特にキシリレングリコール、キシリレンジクロライド、ビスメトキシメチルベンゼンが好ましい。なお、置換基の配置はオルソ、メタ、パラいずれでもかまわないが、耐熱性、機械特性のバランスから特にパラ体が好ましい。)等のキシリレン化合物類、ビフェニルジメタノール、ビスハロゲノメチルビフェニル(ハロゲン:塩素、臭素などが挙げられる。)、ビスアルコキシメチルビフェニル(具体的にはビスメトキシメチルビフェニル、ビスエトキシメチルビフェニル、ビスプロポキシメチルビフェニル、ビスブトキシメチルビフェニル、ビスフェノキシメチルビフェニル、ビスアリルオキシメチルビフェニルなど、炭素数1〜6のアルコキシメチル体など。)等のビフェニルビスメチレン化合物類等のベンジルメチレン化合物、ジビニルベンゼン等のビニルベンゼン構造を有する化合物が挙げられる。
本合成反応においては特にビフェニルジメタノール、ビスクロロメチルビフェニル、ビスメトキシメチルビフェニルが好ましい。Here, as specific examples of the bond-forming compound, aldehydes such as formaldehyde, acetaldehyde, glyoxal, propyl aldehyde, isovaleraldehyde, octyl aldehyde, furfural, benzaldehyde, pyridinecarbaldehyde, acetone, methyl ethyl ketone, cyclopentanone, Ketones such as cyclohexanone, xylylene glycol, xylylene dihalide (halogen: chlorine, bromine, etc.), bisalkoxymethylbenzene (xylylene bisalkyl ether, specifically bismethoxymethylbenzene, bisethoxymethylbenzene) Bispropoxymethylbenzene, bisbutoxymethylbenzene, bisphenoxymethylbenzene, bisallyloxymethylbenzene, etc. In this synthesis reaction, xylylene glycol, xylylene dichloride, and bismethoxymethylbenzene are particularly preferred, and the arrangement of substituents may be any of ortho, meta, and para, but there is a balance between heat resistance and mechanical properties. From xylylene compounds such as biphenyldimethanol, bishalogenomethylbiphenyl (halogen: chlorine, bromine, etc.), bisalkoxymethylbiphenyl (specifically bismethoxymethylbiphenyl, bis Biphenyl bismethylenes such as ethoxymethyl biphenyl, bispropoxymethyl biphenyl, bisbutoxymethyl biphenyl, bisphenoxymethyl biphenyl, bisallyloxymethyl biphenyl, etc. Benzyl methylene compounds of goods, and the like, compounds having a vinyl benzene structure such as divinylbenzene.
In this synthesis reaction, biphenyldimethanol, bischloromethylbiphenyl, and bismethoxymethylbiphenyl are particularly preferable.
本発明の多価フェニレンエーテルノボラック樹脂は、原料ポリ(フェニレンエーテル)樹脂と結合形成化合物とを、溶剤の混合液に、必要に応じて触媒を加えて加熱することにより得られる。
また、原料ポリ(フェニレンエーテル)樹脂と必要に応じて触媒を溶解させた溶液に結合形成化合物を徐々に添加してもよい。反応時間は通常3〜150時間、反応温度は通常40〜150℃である。このようにして得られた多価フェニレンエーテルノボラック樹脂は用途によって、精製せずに用いることもできるが、通常、反応終了後に反応混合物を必要に応じて中和等の処理をしてから、晶析あるいは加熱減圧下において溶媒類を除去する事で精製して各種用途に使用する。また、反応によって、得られる多価フェニレンエーテルノボラック樹脂の平均分子量は大きくなるため、樹脂の軟化点が非常に高くなり、反応容器から取り出すことが困難になることから、以下(a)〜(d)の手法が利用できる。The polyvalent phenylene ether novolak resin of the present invention can be obtained by heating a raw material poly (phenylene ether) resin and a bond-forming compound with a catalyst added to a solvent mixture as necessary.
Further, the bond-forming compound may be gradually added to a solution in which a raw material poly (phenylene ether) resin and a catalyst are dissolved as necessary. The reaction time is usually 3 to 150 hours, and the reaction temperature is usually 40 to 150 ° C. The polyvalent phenylene ether novolak resin thus obtained can be used without being purified depending on the use. Usually, after completion of the reaction, the reaction mixture is neutralized as necessary, and then the crystal It is refined by removing solvents under precipitation or heating under reduced pressure and used for various applications. Further, since the average molecular weight of the polyvalent phenylene ether novolak resin obtained by the reaction is increased, the softening point of the resin becomes very high and it is difficult to take out from the reaction vessel. Therefore, the following (a) to (d) ) Method can be used.
(a)水溶性溶剤で希釈後、水と混合させることで再沈殿することで得る方法。
(b)炭素数1〜4のアルコール類(メタノール、エタノール、プロパノール、ブタノール他)により希釈し、再沈殿することで得る方法。
(c)反応・精製終了後の溶剤に含まれる水のみ除去(加熱減圧等)した後、溶剤カットのワニスとして反応容器から取り出す方法。(樹脂濃度としては、好ましくは10〜90重量%であり、より好ましくは10〜80重量%、特に好ましくは30〜80重量%である。)特に粘度を重要視する場合が多く、その流動性から25℃での粘度が1000Pa・s以下が好ましく、より好ましくは100Pa・s以下である。粘度が高すぎる場合、使用時に流動性が無いことから取出しや、他の樹脂との混合が困難になることがある。なお使用可能な溶剤については後述する(硬化性樹脂組成物ワニスの項に記載の溶剤である。)。
(d)他樹脂(後述する硬化性樹脂組成物用硬化剤の項に記載の樹脂)と混合し、硬化剤組成物として反応容器から取り出す方法。(混合割合は他樹脂と本発明の樹脂の重量比で90:10〜30:70が好ましく、より好ましくは80:20〜30:70である。本発明の樹脂の配合量が少ない場合、誘電特性の大幅な改良は無い。)(A) A method obtained by reprecipitation by diluting with a water-soluble solvent and then mixing with water.
(B) A method obtained by diluting with an alcohol having 1 to 4 carbon atoms (methanol, ethanol, propanol, butanol, etc.) and reprecipitation.
(C) A method of removing only water contained in the solvent after completion of the reaction / purification (heating under reduced pressure, etc.) and then removing it from the reaction vessel as a solvent-cut varnish. (The resin concentration is preferably 10 to 90% by weight, more preferably 10 to 80% by weight, particularly preferably 30 to 80% by weight). The viscosity at 25 ° C. is preferably 1000 Pa · s or less, and more preferably 100 Pa · s or less. If the viscosity is too high, it may be difficult to take out or mix with other resins because it is not fluid during use. In addition, the solvent which can be used is mentioned later (it is a solvent as described in the term of the curable resin composition varnish).
(D) A method of mixing with other resin (the resin described in the section of curing agent for curable resin composition described later) and taking it out from the reaction vessel as a curing agent composition. (The mixing ratio is preferably 90:10 to 30:70, more preferably 80:20 to 30:70 in terms of the weight ratio of the other resin and the resin of the present invention. There is no significant improvement in characteristics.)
また、原料ポリ(フェニレンエーテル)樹脂と結合形成化合物との反応モル比(水酸基当量比)は1.2:1〜20:1が好ましく、より好ましくは1.5:1〜15:1、特に好ましくは1.5:1〜10:1である。反応モル比が1.2:1を下回る、すなわち結合形成化合物1に対し、原料ポリ(フェニレンエーテル)樹脂が1.2未満である場合、生成する多価フェニレンエーテルノボラック樹脂の分子量が大きくなりすぎてしまうため、溶剤への溶解性、また他の樹脂との相溶性が悪くなることがある。また、20:1を上回る、すなわち、結合形成化合物1に対し、原料ポリ(フェニレンエーテル)樹脂が20を超える場合、耐熱性に乏しくなることがある。 Further, the reaction molar ratio (hydroxyl equivalent ratio) between the raw material poly (phenylene ether) resin and the bond-forming compound is preferably 1.2: 1 to 20: 1, more preferably 1.5: 1 to 15: 1, particularly Preferably it is 1.5: 1-10: 1. When the reaction molar ratio is less than 1.2: 1, that is, when the raw material poly (phenylene ether) resin is less than 1.2 with respect to the bond-forming compound 1, the molecular weight of the polyvalent phenylene ether novolak resin to be formed becomes too large. Therefore, the solubility in a solvent and the compatibility with other resins may deteriorate. Moreover, when it exceeds 20: 1, ie, when the raw material poly (phenylene ether) resin exceeds 20 with respect to the bond-forming compound 1, heat resistance may be poor.
本発明の多価フェニレンエーテルノボラック樹脂の合成において使用できる溶媒としては、トルエン、キシレン、メチルイソブチルケトン、アノン、シクロペンタノン、メチルエチルケトンなどが挙げられるがこれらに限定されるものではなく、単独でも2種以上併用してもよい。併用できる溶剤としては上記それぞれに加え、メタノール、エタノール、イソプロパノール、ブタノール等のアルコール類、アセトン等のケトン類、酢酸エチル、酢酸ブチル、カルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート等のエステル類、テトラヒドロフラン、ジオキサン等のエーテル類、N−メチルピロリドン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等の含窒素溶剤などが挙げられる。溶媒の使用量は原料ポリ(フェニレンエーテル)樹脂と結合形成化合物との合計量100重量部に対し、通常5〜500重量部、好ましくは10〜400重量部の範囲である。 Solvents that can be used in the synthesis of the polyvalent phenylene ether novolak resin of the present invention include toluene, xylene, methyl isobutyl ketone, anone, cyclopentanone, methyl ethyl ketone, and the like. Two or more species may be used in combination. Solvents that can be used in combination, in addition to the above, alcohols such as methanol, ethanol, isopropanol, butanol, ketones such as acetone, esters such as ethyl acetate, butyl acetate, carbitol acetate, propylene glycol monomethyl ether acetate, tetrahydrofuran, Examples include ethers such as dioxane, nitrogen-containing solvents such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide. The amount of the solvent used is usually in the range of 5 to 500 parts by weight, preferably 10 to 400 parts by weight with respect to 100 parts by weight of the total amount of the raw material poly (phenylene ether) resin and the bond-forming compound.
触媒としては、基本的には酸性触媒を用いることが好ましい。結合形成化合物がベンジルハライドの場合は触媒の添加がなくともスムーズに反応を進めることができ、後の精製のしやすさの観点から触媒無し、もしくはほとんど使用しない方が好ましい。触媒を使用する場合、酸性触媒の具体例としては塩酸、硫酸、リン酸等の鉱酸類;シュウ酸、トルエンスルホン酸、酢酸等の有機酸類;タングステン酸等のヘテロポリ酸、活性白土、無機酸、塩化第二錫、塩化亜鉛、塩化第二鉄等、その他酸性を示す有機、無機酸塩類、等のノボラック樹脂製造用に通常使用される酸性触媒などが挙げられる。これら触媒は、前述に挙げた物に限定されるものではなく、単独でも2種以上を併用してもよい。触媒の使用量は、原料ポリ(フェニレンエーテル)樹脂に対し、通常0.005〜2.0倍モル、好ましくは0.01〜1.1倍モルの範囲、もしくは原料ポリ(フェニレンエーテル)樹脂100gに対し0.1〜50gが好ましく、より好ましくは0.3〜20部である。触媒量が少ないと反応の進行が遅くなる。また高温での反応が必要になる、反応が最後まで進まない等の課題が生じ、好ましく無い。また、触媒量が多すぎる場合、中和・精製等の後処理において多大な労力がかかることがある。
なお、反応により腐食性ガスが生成する場合は、引圧、もしくは窒素等の不活性ガスを送り込むことにより、系内から排出させることが好ましい。As the catalyst, it is basically preferable to use an acidic catalyst. When the bond-forming compound is benzyl halide, the reaction can proceed smoothly without the addition of a catalyst. From the viewpoint of ease of subsequent purification, it is preferable to use no catalyst or hardly use it. When using the catalyst, specific examples of the acidic catalyst include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as oxalic acid, toluenesulfonic acid and acetic acid; heteropolyacids such as tungstic acid, activated clay, inorganic acids, Examples include stannic chloride, zinc chloride, ferric chloride, and other acidic catalysts usually used for the production of novolak resins such as organic and inorganic acid salts showing acidity. These catalysts are not limited to those mentioned above, and may be used alone or in combination of two or more. The amount of the catalyst used is usually in the range of 0.005 to 2.0 times mol, preferably 0.01 to 1.1 times mol, or 100 g of material poly (phenylene ether) resin relative to the material poly (phenylene ether) resin. The amount is preferably 0.1 to 50 g, more preferably 0.3 to 20 parts. If the amount of catalyst is small, the progress of the reaction is slow. Moreover, problems such as the need for a reaction at a high temperature and the reaction not proceeding to the end are not preferable. Moreover, when there is too much catalyst amount, a great amount of labor may be applied in post-treatments such as neutralization and purification.
In addition, when corrosive gas produces | generates by reaction, it is preferable to make it exhaust from the inside of a system by sending inactive gas, such as drawing pressure or nitrogen.
このようにして得られる多価フェニレンエーテルノボラック樹脂は、下記式(A)で示されるような構造式で代表され、この代表構造式の具体例を以下説明する。
得られる多価フェニレンエーテルノボラック樹脂は、下記Bに例示的に記載されているポリ(フェニレンエーテル)樹脂のベンゼン骨格が下記Aで例示的に記載されている連結基によって連結されており、前記連結基はポリ(フェニレンエーテル)樹脂の同一分子中のベンゼン骨格同士で、或いは2つ以上のポリ(フェニレンエーテル)樹脂の分子のベンゼン骨格同士間を連結している。
そして、連結基周辺の部分構造は例えば、下記式(A)のような構造となる。尚、下記ベンゼン骨格は、ポリ(フェニレンエーテル)樹脂分子中のベンゼン骨格を表している。The polyvalent phenylene ether novolak resin thus obtained is represented by a structural formula represented by the following formula (A), and specific examples of this representative structural formula will be described below.
The resulting polyvalent phenylene ether novolak resin is such that the benzene skeleton of the poly (phenylene ether) resin described in B below is connected by the connecting group described in A below, The groups connect the benzene skeletons in the same molecule of the poly (phenylene ether) resin or the benzene skeletons of two or more poly (phenylene ether) resin molecules.
And the partial structure around a coupling group becomes a structure like following formula (A), for example. The following benzene skeleton represents a benzene skeleton in a poly (phenylene ether) resin molecule.
(上記式中、Pはポリ(フェニレンエーテル)樹脂の残基を、Xは下記式(1)で表される連結基を、Rは水素原子または炭素数1〜3のアルキル基を、*は水素原子または上記Xを示し、nは1〜2の整数を表す。) (In the above formula, P is a residue of a poly (phenylene ether) resin, X is a linking group represented by the following formula (1), R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, * is A hydrogen atom or the above X is shown, and n represents an integer of 1 to 2.)
ここで、上記のポリ(フェニレンエーテル)樹脂の残基は、さらに別のベンゼン骨格でXを介して、ポリ(フェニレンエーテル)樹脂分子中のベンゼン骨格と連結し得る。 Here, the residue of the above poly (phenylene ether) resin can be linked to the benzene skeleton in the poly (phenylene ether) resin molecule via X in another benzene skeleton.
このようにして得られる本発明の多価フェニレンエーテルノボラック樹脂は褐色の樹脂状(もしくは紛体)で、有機溶剤に可溶であり、ワニスとしても取り扱うことのできる樹脂となる。
このようにして得られる本発明の多価フェニレンエーテルノボラック樹脂の水酸基当量は400〜6000が好ましく、500〜5000が特に好ましい。
重量平均分子量としては、600〜50000が好ましく、700〜25000が特に好ましい。The polyphenylene ether novolak resin of the present invention thus obtained is a brown resin (or powder), is soluble in an organic solvent, and can be handled as a varnish.
The thus obtained polyvalent phenylene ether novolak resin of the present invention preferably has a hydroxyl group equivalent of 400 to 6000, particularly preferably 500 to 5000.
As a weight average molecular weight, 600-50000 are preferable and 700-25000 are especially preferable.
本発明の多価フェニレンエーテルノボラック樹脂は、そのままで熱可塑性プラスチック(もしくはその原料)として使用したり、熱可塑性プラスチックと混合して特性改善を行ったり、エポキシ樹脂の原料やその硬化剤として使用したりすることもできる。 The polyvalent phenylene ether novolak resin of the present invention can be used as it is as a thermoplastic (or its raw material), mixed with a thermoplastic to improve its properties, or used as a raw material for an epoxy resin and its curing agent. You can also.
以下、本発明の多価フェニレンエーテルノボラック樹脂を含む本発明のエポキシ樹脂組成物(以下、硬化性樹脂組成物とも称する)について記載する。本発明の硬化性樹脂組成物においては、エポキシ樹脂を必須成分として使用する。 Hereinafter, it describes about the epoxy resin composition (henceforth a curable resin composition) of this invention containing the polyhydric phenylene ether novolak resin of this invention. In the curable resin composition of the present invention, an epoxy resin is used as an essential component.
本発明の硬化性樹脂組成物においては、エポキシ樹脂−硬化剤を必須成分とする組成物であり、多価フェニレンエーテルノボラック樹脂をエポキシ樹脂の硬化剤として必ず含有する。また、必要に応じて硬化促進剤を含有する。 The curable resin composition of the present invention is a composition containing an epoxy resin-curing agent as an essential component and always contains a polyvalent phenylene ether novolak resin as a curing agent for the epoxy resin. Moreover, a hardening accelerator is contained as needed.
本発明の硬化性樹脂組成物において使用できるエポキシ樹脂の具体例としては、ノボラック型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂などが挙げられる。具体的には、ビスフェノールA、ビスフェノールS、チオジフェノール、フルオレンビスフェノール、テルペンジフェノール、4,4’−ビフェノール、2,2’−ビフェノール、3,3’,5,5’−テトラメチル−[1,1’−ビフェニル]−4,4’−ジオール、ハイドロキノン、レゾルシン、ナフタレンジオール、トリス−(4−ヒドロキシフェニル)メタン、1,1,2,2−テトラキス(4−ヒドロキシフェニル)エタン、フェノール類(フェノール、アルキル置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、ジヒドロキシナフタレン等)とホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、p−ヒドロキシベンズアルデヒド、o−ヒドロキシベンズアルデヒド、p−ヒドロキシアセトフェノン、o−ヒドロキシアセトフェノン、ジシクロペンタジエン、フルフラール、4,4’−ビス(クロルメチル)−1,1’−ビフェニル、4,4’−ビス(メトキシメチル)−1,1’−ビフェニル、1,4−ビス(クロロメチル)ベンゼン、1,4−ビス(メトキシメチル)ベンゼン等との重縮合物及びこれらの変性物、テトラブロモビスフェノールA等のハロゲン化ビスフェノール類、アルコール類から誘導されるグリシジルエーテル化物、脂環式エポキシ樹脂、グリシジルアミン系エポキシ樹脂、グリシジルエステル系エポキシ樹脂等、シルセスキオキサン系のエポキシ樹脂(鎖状、環状、ラダー状、あるいはそれら少なくとも2種以上の混合構造のシロキサン構造にグリシジル基、および/またはエポキシシクロヘキサン構造を有するエポキシ樹脂)等の固形または液状エポキシ樹脂が挙げられるが、これらに限定されるものではない。 Specific examples of epoxy resins that can be used in the curable resin composition of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and the like. It is done. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols Silsesquioxane epoxy resin (chain, cyclic, ladder, or a mixed siloxane structure of at least two of them) such as a compound, alicyclic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, etc. Has glycidyl group and / or epoxycyclohexane structure Solid or liquid epoxy resin having an epoxy resin) and the like although not limited thereto.
本発明の硬化性樹脂組成物が含有する硬化剤としては、前述の本発明の多価フェニレンエーテルノボラック樹脂以外に他の硬化剤を併用することが出来る。併用する場合は、前述の本発明の多価フェニレンエーテルノボラック樹脂と他の硬化剤との硬化剤組成物として使用することができる。併用する場合、本発明の多価ポリフェニレンエーテルノボラック樹脂の全エポキシ樹脂組成物中に占める割合は、30重量%以上が好ましく、特に40重量%以上が好ましい。 As the curing agent contained in the curable resin composition of the present invention, other curing agents can be used in combination with the polyphenylene ether novolak resin of the present invention described above. When used in combination, it can be used as a curing agent composition of the above-described polyphenylene ether novolak resin of the present invention and another curing agent. When used together, the proportion of the polyvalent polyphenylene ether novolak resin of the present invention in the total epoxy resin composition is preferably 30% by weight or more, particularly preferably 40% by weight or more.
併用し得る硬化剤としては、例えばフェノール樹脂、フェノール系化合物、アミン系化合物、酸無水物系化合物、アミド系化合物、カルボン酸系化合物などが挙げられる。
用いうる硬化剤の具体例としては以下の通りである。
フェノール樹脂、フェノール化合物;ビスフェノールA、ビスフェノールF、ビスフェノールS、フルオレンビスフェノール、テルペンジフェノール、4,4’−ビフェノール、2,2’−ビフェノール、3,3’,5,5’−テトラメチル−[1,1’−ビフェニル]−4,4’−ジオール、ハイドロキノン、レゾルシン、ナフタレンジオール、トリス−(4−ヒドロキシフェニル)メタン、1,1,2,2−テトラキス(4−ヒドロキシフェニル)エタン、フェノール類(フェノール、アルキル置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、ジヒドロキシナフタレン等)とホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、p−ヒドロキシベンズアルデヒド、o−ヒドロキシベンズアルデヒド、p−ヒドロキシアセトフェノン、o−ヒドロキシアセトフェノン、ジシクロペンタジエン、フルフラール、4,4’−ビス(クロロメチル)−1,1’−ビフェニル、4,4’−ビス(メトキシメチル)−1,1’−ビフェニル、1,4’−ビス(クロロメチル)ベンゼン、1,4’−ビス(メトキシメチル)ベンゼン等との重縮合物及びこれらの変性物、テトラブロモビスフェノールA等のハロゲン化ビスフェノール類、テルペンとフェノール類の縮合物などのポリフェノール類が挙げられるが、これらに限定されるものではない。これらは単独で用いてもよく、2種以上を用いてもよい。Examples of the curing agent that can be used in combination include a phenol resin, a phenol compound, an amine compound, an acid anhydride compound, an amide compound, and a carboxylic acid compound.
Specific examples of the curing agent that can be used are as follows.
Phenol resin, phenol compound; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hy Loxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, Polycondensates with 1,4′-bis (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene and their modified products, halogenated bisphenols such as tetrabromobisphenol A, terpenes and phenols However, the present invention is not limited to these. These may be used alone or in combination of two or more.
好ましいフェノール樹脂としては、誘電率の面からフェノールアラルキル樹脂(芳香族アルキレン構造を有する樹脂)が挙げられ、特に好ましくはフェノール、ナフトール、クレゾールから選ばれる少なくとも一種を有する構造であり、そのリンカーとなるアルキレン部が、ベンゼン構造、ビフェニル構造、ナフタレン構造から選ばれる少なくとも一種であることを特徴とする樹脂(具体的にはザイロック、ナフトールザイロック、フェノールビフェニレンノボラック樹脂、クレゾール−ビフェニレンノボラック樹脂、フェノール−ナフタレンノボラック樹脂などが挙げられる。)である。 Preferred phenol resins include phenol aralkyl resins (resins having an aromatic alkylene structure) in terms of dielectric constant, and particularly preferred is a structure having at least one selected from phenol, naphthol, and cresol, and serves as the linker. A resin characterized in that the alkylene part is at least one selected from a benzene structure, a biphenyl structure, and a naphthalene structure (specifically, zylock, naphthol zylock, phenol biphenylene novolak resin, cresol-biphenylene novolak resin, phenol-naphthalene) And novolak resin.).
アミン系化合物、アミド系化合物;ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、ジシアンジアミド、リノレン酸の2量体とエチレンジアミンより合成されるポリアミド樹脂などの含窒素化合物が挙げられるが、これらに限定されるものではない。これらは単独で用いてもよく、2種以上を用いてもよい。 Amine compounds, amide compounds; diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, nitrogen-containing compounds such as polyamide resins synthesized from linolenic acid and ethylenediamine, It is not limited to these. These may be used alone or in combination of two or more.
酸無水物系化合物、カルボン酸系化合物;無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、無水ナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ブタンテトラカルボン酸無水物、ビシクロ[2,2,1]ヘプタン−2,3−ジカルボン酸無水物、メチルビシクロ[2,2,1]ヘプタン−2,3−ジカルボン酸無水物、シクロヘキサン−1,3,4−トリカルボン酸−3,4−無水物、などの酸無水物;各種アルコール、カルビノール変性シリコーン、と前述の酸無水物との付加反応により得られるカルボン酸樹脂が挙げられるが、これらに限定されるものではない。これらは単独で用いてもよく、2種以上を用いてもよい。 Acid anhydride compounds, carboxylic acid compounds; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydro Phthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2, Acid anhydrides such as 3-dicarboxylic acid anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride; by addition reaction of various alcohols, carbinol-modified silicone, and the above-mentioned acid anhydrides Although the obtained carboxylic acid resin is mentioned, it is not limited to these. These may be used alone or in combination of two or more.
その他の併用し得る硬化剤としては、イミダゾール、トリフルオロボラン−アミン錯体、グアニジン誘導体の化合物などが挙げられるが、これらに限定されるものではない。これらは単独で用いてもよく、2種以上を用いてもよい。 Other curing agents that can be used in combination include, but are not limited to, imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, and the like. These may be used alone or in combination of two or more.
本発明の硬化性樹脂組成物において硬化剤の使用量は、全エポキシ樹脂のエポキシ基1当量に対してその官能基(水酸基)当量で0.7〜1.2当量が好ましい。エポキシ基1当量に対して、0.7当量に満たない場合、あるいは1.2当量を超える場合、いずれも硬化が不完全となり良好な硬化物性が得られないことがある。 In the curable resin composition of the present invention, the amount of the curing agent used is preferably 0.7 to 1.2 equivalents in terms of its functional group (hydroxyl group) equivalent to 1 equivalent of the epoxy groups of all epoxy resins. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
本発明の硬化性樹脂組成物においては、硬化剤とともに硬化促進剤を併用しても差し支えない。用い得る硬化促進剤の具体例としては、2−メチルイミダゾール、2−エチルイミダゾール、2−エチル−4−メチルイミダゾール等のイミダゾ−ル類、2−(ジメチルアミノメチル)フェノール、1,8−ジアザ−ビシクロ(5,4,0)ウンデセン−7等の第3級アミン類、トリフェニルホスフィン等のホスフィン類、テトラブチルアンモニウム塩、トリイソプロピルメチルアンモニウム塩、トリメチルデカニルアンモニウム塩、セチルトリメチルアンモニウム塩などの4級アンモニウム塩、トリフェニルベンジルフォスフォニウム塩、トリフェニルエチルフォスフォニウム塩、テトラブチルフォスフォニウム塩などの4級フォスフォニウム塩が挙げられる。(4級塩のカウンターイオンはハロゲン、有機酸イオン、水酸化物イオンなど、特に指定は無いが、特に有機酸イオン、水酸化物イオンが好ましい。)、オクチル酸スズ等の金属化合物等が挙げられる。硬化促進剤を用いる場合は、エポキシ樹脂100重量部に対して0.01〜5.0重量部が必要に応じ用いられる。 In the curable resin composition of the present invention, a curing accelerator may be used in combination with the curing agent. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, and 1,8-diaza. -Tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, etc. And quaternary ammonium salts, triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, tetrabutylphosphonium salts, and the like. (The counter ion of the quaternary salt is not particularly specified, such as halogen, organic acid ion, hydroxide ion, etc., but organic acid ion and hydroxide ion are particularly preferable), metal compounds such as tin octylate, etc. It is done. When using a hardening accelerator, 0.01-5.0 weight part is used as needed with respect to 100 weight part of epoxy resins.
本発明の硬化性樹脂組成物には、リン含有化合物を難燃性付与成分として含有させることもできる。リン含有化合物としては反応型のものでも添加型のものでもよい。リン含有化合物の具体例としては、トリメチルホスフェート、トリエチルホスフェート、トリクレジルホスフェート、トリキシリレニルホスフェート、クレジルジフェニルホスフェート、クレジル−2,6−ジキシリレニルホスフェート、1,3−フェニレンビス(ジキシリレニルホスフェート)、1,4−フェニレンビス(ジキシリレニルホスフェート)、4,4'−ビフェニル(ジキシリレニルホスフェート)等のリン酸エステル類;9,10−ジヒドロ−9−オキサ−10−ホスファフェナントレン−10−オキサイド、10(2,5−ジヒドロキシフェニル)−10H−9−オキサ−10−ホスファフェナントレン−10−オキサイド等のホスファン類;エポキシ樹脂と前記ホスファン類の活性水素とを反応させて得られるリン含有エポキシ化合物、赤リン等が挙げられるが、リン酸エステル類、ホスファン類またはリン含有エポキシ化合物が好ましく、1,3−フェニレンビス(ジキシリレニルホスフェート)、1,4−フェニレンビス(ジキシリレニルホスフェート)、4,4'−ビフェニル(ジキシリレニルホスフェート)またはリン含有エポキシ化合物が特に好ましい。リン含有化合物の含有量はリン含有化合物/全エポキシ樹脂=0.1〜0.6(重量比)が好ましい。0.1以下では難燃性が不十分になることがあり、0.6以上では硬化物の吸湿性、誘電特性が低下することがある。 The curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes A phosphorus-containing product obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned, and phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy may be insufficient, and if it is 0.6 or more, the hygroscopicity and dielectric properties of the cured product may be deteriorated.
さらに本発明の硬化性樹脂組成物には、必要に応じて酸化防止剤を添加しても構わない。使用できる酸化防止剤としては、フェノール系、イオウ系、リン系酸化防止剤が挙げられる。酸化防止剤は単独で又は2種以上を組み合わせて使用できる。酸化防止剤の使用量は、本発明の硬化性樹脂組成物中の樹脂成分100重量部に対して、通常0.008〜1重量部、好ましくは0.01〜0.5重量部である。 Furthermore, you may add antioxidant to the curable resin composition of this invention as needed. Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more. The usage-amount of antioxidant is 0.008-1 weight part normally with respect to 100 weight part of resin components in the curable resin composition of this invention, Preferably it is 0.01-0.5 weight part.
フェノール系酸化防止剤の具体例として、2,6−ジ−t−ブチル−p−クレゾール、ブチル化ヒドロキシアニソール、2,6−ジ−t−ブチル−p−エチルフェノール、ステアリル−β−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート、イソオクチル−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート、2,4−ビス−(n−オクチルチオ)−6−(4−ヒドロキシ−3,5−ジ−t−ブチルアニリノ)−1,3,5−トリアジン、2,4−ビス[(オクチルチオ)メチル]−o−クレゾール等のモノフェノール類;2,2’−メチレンビス(4−メチル−6−t−ブチルフェノール)、2,2’−メチレンビス(4−エチル−6−t−ブチルフェノール)、4,4’−チオビス(3−メチル−6−t−ブチルフェノール)、4,4’−ブチリデンビス(3−メチル−6−t−ブチルフェノール)、トリエチレングリコール−ビス[3−(3−t−ブチル−5−メチル−4−ヒドロキシフェニル)プロピオネート]、1,6−ヘキサンジオール−ビス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]、N,N’−ヘキサメチレンビス(3,5−ジ−t−ブチル−4−ヒドロキシ−ヒドロシンナマミド)、2,2−チオ−ジエチレンビス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]、3,5−ジ−t−ブチル−4−ヒドロキシベンジルフォスフォネート−ジエチルエステル、3,9−ビス[1,1−ジメチル−2−{β−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオニルオキシ}エチル]2,4,8,10−テトラオキサスピロ[5,5]ウンデカン、ビス(3,5−ジ−t−ブチル−4−ヒドロキシベンジルスルホン酸エチル)カルシウム等のビスフェノール類;1,1,3−トリス(2−メチル−4−ヒドロキシ−5−t−ブチルフェニル)ブタン、1,3,5−トリメチル−2,4,6−トリス(3,5−ジ−t−ブチル−4−ヒドロキシベンジル)ベンゼン、テトラキス−[メチレン−3−(3’,5’−ジ−t−ブチル−4’−ヒドロキシフェニル)プロピオネート]メタン、ビス[3,3’−ビス−(4’−ヒドロキシ−3’−t−ブチルフェニル)ブチリックアシッド]グリコールエステル、トリス−(3,5−ジ−t−ブチル−4−ヒドロキシベンジル)−イソシアヌレイト、1,3,5−トリス(3’,5’−ジ−t−ブチル−4’−ヒドロキシベンジル)−S−トリアジン−2,4,6−(1H,3H,5H)トリオン、トコフェノール等の高分子型フェノール類が例示される。 Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2,2 '-Methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3-me 6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) ) Propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t) -Butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,5-di-t -Butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methyl Ruphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bisphenols such as bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate) calcium 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4 '-Hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanate Nurate, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol And the like.
イオウ系酸化防止剤の具体例として、ジラウリル−3,3’−チオジプロピオネート、ジミリスチル−3,3’−チオジプロピオネート、ジステアリル−3,3’−チオジプロピオネート等が例示される。 Specific examples of the sulfur antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. The
リン系酸化防止剤の具体例として、トリフェニルホスファイト、ジフェニルイソデシルホスファイト、フェニルジイソデシルホスファイト、トリス(ノニルフェニル)ホスファイト、ジイソデシルペンタエリスリトールホスファイト、トリス(2,4−ジ−t−ブチルフェニル)ホスファイト、サイクリックネオペンタンテトライルビス(オクタデシル)ホスファイト、サイクリックネオペンタンテトライルビ(2,4−ジ−t−ブチルフェニル)ホスファイト、サイクリックネオペンタンテトライルビ(2,4−ジ−t−ブチル−4−メチルフェニル)ホスファイト、ビス[2−t−ブチル−6−メチル−4−{2−(オクタデシルオキシカルボニル)エチル}フェニル]ヒドロゲンホスファイト等のホスファイト類;9,10−ジヒドロ−9−オキサ−10−ホスファフェナントレン−10−オキサイド、10−(3,5−ジ−t−ブチル−4−ヒドロキシベンジル)−9,10−ジヒドロ−9−オキサ−10−ホスファフェナントレン−10−オキサイド、10−デシロキシ−9,10−ジヒドロ−9−オキサ−10−ホスファフェナントレン−10−オキサイド等のオキサホスファフェナントレンオキサイド類などが例示される。 Specific examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. 9,10-dihydro 9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxaphosphaphenanthrene oxides such as 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are exemplified.
これらの酸化防止剤はそれぞれ単独で使用できるが、2種以上を組み合わせて併用しても構わない。特に本発明においてはリン系の酸化防止剤が好ましい。 These antioxidants can be used alone, but two or more of them may be used in combination. In the present invention, a phosphorus-based antioxidant is particularly preferable.
さらに本発明の硬化性樹脂組成物には、必要に応じて光安定剤を添加しても構わない。
光安定剤としては、ヒンダートアミン系の光安定剤、特にHALS等が好適である。HALSとしては特に限定されるものではないが、代表的なものとしては、ジブチルアミン・1,3,5−トリアジン・N,N’―ビス(2,2,6,6−テトラメチル−4−ピペリジル−1,6−ヘキサメチレンジアミンとN−(2,2,6,6−テトラメチル−4−ピペリジル)ブチルアミンの重縮合物、コハク酸ジメチル−1−(2−ヒドロキシエチル)−4−ヒドロキシ−2,2,6,6−テトラメチルピペリジン重縮合物、ポリ〔{6−(1,1,3,3−テトラメチルブチル)アミノ−1,3,5−トリアジン−2,4−ジイル}{(2,2,6,6−テトラメチル−4−ピペリジル)イミノ}ヘキサメチレン{(2,2,6,6−テトラメチル−4−ピペリジル)イミノ}〕、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)〔〔3,5−ビス(1,1−ジメチルエチル)−4−ヒドリキシフェニル〕メチル〕ブチルマロネート、ビス(2,2,6,6−テトラメチル−4−ピペリジル)セバケート、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)セバケート、ビス(1−オクチロキシ−2,2,6,6−テトラメチル−4−ピペリジル)セバケート、2−(3,5−ジ−t−ブチル−4−ヒドロキシベンジル)−2−n−ブチルマロン酸ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)等が挙げられる。HALSは1種のみが用いられても良いし、2種類以上が併用されても良い。Furthermore, you may add a light stabilizer to the curable resin composition of this invention as needed.
As the light stabilizer, hindered amine-based light stabilizers, particularly HALS and the like are suitable. HALS is not particularly limited, but representative examples include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (1,2,2, 6,6-pentamethyl-4-pi Peridyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), etc. Only one HALS is used. Alternatively, two or more types may be used in combination.
さらに本発明の硬化性樹脂組成物には、必要に応じてバインダー樹脂を配合することも出来る。バインダー樹脂としてはブチラール系樹脂、アセタール系樹脂、アクリル系樹脂、エポキシ−ナイロン系樹脂、NBR−フェノール系樹脂、エポキシ−NBR系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、シリコーン系樹脂などが挙げられるが、これらに限定されるものではない。バインダー樹脂の配合量は、硬化物の難燃性、耐熱性を損なわない範囲であることが好ましく、樹脂成分100重量部に対して通常0.05〜50重量部、好ましくは0.05〜20重量部が必要に応じて用いられる。 Furthermore, binder resin can also be mix | blended with the curable resin composition of this invention as needed. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts per 100 parts by weight of the resin component. Part by weight is used as needed.
本発明の硬化性樹脂組成物には、必要に応じて無機充填剤を添加することができる。無機充填剤としては、結晶シリカ、溶融シリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、炭化ケイ素、窒化ケイ素、窒化ホウ素、ジルコニア、フォステライト、ステアタイト、スピネル、チタニア、タルク等の粉体またはこれらを球形化したビーズ等が挙げられるが、これらに限定されるものではない。これらは単独で用いてもよく、2種以上を用いてもよい。これら無機充填剤の含有量は、本発明の硬化性樹脂組成物中において0〜95重量%を占める量が用いられる。更に本発明の硬化性樹脂組成物には、シランカップリング剤、ステアリン酸、パルミチン酸、ステアリン酸亜鉛、ステアリン酸カルシウム等の離型剤、界面活性剤、染料、顔料、紫外線吸収剤等の種々の配合剤、各種熱硬化性樹脂を添加することができる。 An inorganic filler can be added to the curable resin composition of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the curable resin composition of the present invention. Furthermore, the curable resin composition of the present invention includes various agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers. A compounding agent and various thermosetting resins can be added.
本発明の硬化性樹脂組成物は、各成分を均一に混合することにより得られる。本発明の硬化性樹脂組成物は従来知られている方法と同様の方法で容易にその硬化物とすることができる。例えば本発明のポリフェニレンエーテルノボラック樹脂とエポキシ樹脂並びに必要により硬化促進剤、リン含有化合物、バインダー樹脂、無機充填材及び配合剤とを必要に応じて押出機、ニーダ、ロール等を用いて均一になるまで充分に混合して硬化性樹脂組成物を得、その硬化性樹脂組成物をポッティング、溶融後(液状の場合は溶融無しに)注型あるいはトランスファー成型機などを用いて成型し、さらに80〜200℃で2〜10時間加熱することにより本発明の硬化物を得ることができる。 The curable resin composition of this invention is obtained by mixing each component uniformly. The curable resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the polyphenylene ether novolak resin and epoxy resin of the present invention and, if necessary, the curing accelerator, phosphorus-containing compound, binder resin, inorganic filler and compounding agent are made uniform using an extruder, kneader, roll or the like as necessary. Are mixed sufficiently until a curable resin composition is obtained, and the curable resin composition is potted, melted (without melting in the case of a liquid), molded using a casting or transfer molding machine, and further 80 to The cured product of the present invention can be obtained by heating at 200 ° C. for 2 to 10 hours.
また本発明の硬化性樹脂組成物を必要に応じてトルエン、キシレン、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジメチルホルムアミド、ジメチルアセトアミド、N−メチルピロリドン等の溶剤に溶解させ、硬化性樹脂組成物ワニスとし、ガラス繊維、カーボン繊維、ポリエステル繊維、ポリアミド繊維、アルミナ繊維、紙などの基材に含浸させて加熱乾燥して得たプリプレグを熱プレス成形することにより、本発明の硬化性樹脂組成物Aの硬化物とすることができる。この際の溶剤は、本発明の硬化性樹脂組成物と該溶剤の混合物中で通常10〜70重量%、好ましくは15〜70重量%を占める量を用いる。また液状組成物であれば、そのまま例えば、RTM方式でカーボン繊維を含有するエポキシ樹脂硬化物を得ることもできる。 Further, the curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone as necessary to obtain a curable resin composition varnish. A prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper and drying by heating is subjected to hot press molding, whereby the curable resin composition A of the present invention is prepared. It can be a cured product. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Moreover, if it is a liquid composition, the epoxy resin hardened | cured material which contains a carbon fiber by the RTM system as it is can also be obtained as it is.
また本発明の硬化性樹脂組成物をフィルム型組成物の改質剤としても使用できる。具体的にはB−ステージにおけるフレキ性等を向上させる場合に用いることができる。このようなフィルム型の樹脂組成物は、本発明の硬化性樹脂組成物を前記硬化性樹脂組成物ワニスとして剥離フィルム上に塗布し、加熱下で溶剤を除去した後、Bステージ化を行うことによりシート状の接着剤として得られる。このシート状接着剤は多層基板などにおける層間絶縁層として使用することが出来る。 Moreover, the curable resin composition of this invention can be used also as a modifier of a film type composition. Specifically, it can be used to improve the flexibility of the B-stage. Such a film-type resin composition is formed by applying the curable resin composition of the present invention on the release film as the curable resin composition varnish, removing the solvent under heating, and then performing B-stage. To obtain a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.
本発明の硬化性樹脂組成物は、エポキシ樹脂が使用される一般の用途が挙げられ、例えば、接着剤、塗料、コーティング剤、成形材料(シート、フィルム、FRP等を含む)、絶縁材料(プリント基板、電線被覆等を含む)、封止剤の他、他樹脂等への添加剤等が挙げられる。接着剤としては、土木用、建築用、自動車用、一般事務用、医療用の接着剤の他、電子材料用の接着剤が挙げられる。これらのうち電子材料用の接着剤としては、ビルドアップ基板等の多層基板の層間接着剤、ダイボンディング剤、アンダーフィル等の半導体用接着剤、BGA補強用アンダーフィル、異方性導電性フィルム(ACF)、異方性導電性ペースト(ACP)等の実装用接着剤等が挙げられる。 The curable resin composition of the present invention includes general uses in which an epoxy resin is used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (prints) In addition to a sealing agent, an additive to other resins and the like are included. Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).
封止剤、基板としては、コンデンサ、トランジスタ、ダイオード、発光ダイオード、IC、LSIなど用のポッティング、ディッピング、トランスファーモールド封止、IC、LSI類のCOB、COF、TABなど用のといったポッティング封止、フリップチップなどの用のアンダーフィル、QFP、BGA、CSPなどのICパッケージ類実装時の封止(補強用アンダーフィルを含む)およびパッケージ基板などを挙げることができる。またネットワーク基板や、モジュール基板といった機能性が求められる基板用途へも好適である。 As sealing agent and substrate, potting sealing for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, ICs, LSIs for COB, COF, TAB, etc. Examples include underfill for flip chip, sealing (including reinforcing underfill) and package substrate when mounting IC packages such as QFP, BGA, and CSP. Moreover, it is suitable also for the board | substrate use with which functionality, such as a network board | substrate and a module board, is calculated | required.
次に本発明を実施例により更に具体的に説明するが、以下において部は特に断わりのない限り重量部である。尚、本発明はこれら実施例に限定されるものではない。
以下に実施例で用いた各種分析方法について記載する。
エポキシ当量: JIS K 7236 (ISO 3001) に準拠
ICI溶融粘度: JIS K 7117−2 (ISO 3219) に準拠
軟化点: JIS K 7234 に準拠
全塩素: JIS K 7243−3 (ISO 21672−3) に準拠
GPC:
カラム(Shodex KF−603、KF−602.5、KF−602、KF−601x2)
連結溶離液はテトラヒドロフラン
流速は0.5ml/min.
カラム温度は40℃
検出:RI(示差屈折検出器)EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.
The various analysis methods used in the examples are described below.
Epoxy equivalent: Conforms to JIS K 7236 (ISO 3001)
ICI melt viscosity: compliant with JIS K 7117-2 (ISO 3219) Softening point: compliant with JIS K 7234 Total chlorine: compliant with JIS K 7243-3 (ISO 21672-3) GPC:
Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2)
The coupled eluent is tetrahydrofuran. The flow rate is 0.5 ml / min.
Column temperature is 40 ° C
Detection: RI (differential refraction detector)
以下、実施例、比較例により本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
(実施例1)
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながらポリフェニレンエーテル樹脂(サビック製 MX90-100、GPCチャートにおいてMn=2066、Mw=3553、Mz=5951)175部、p−キシリレングリコール(東京化成製 試薬)9.6部、トルエン(純正化学製 試薬)300部、パラトルエンスルホン酸・一水和物(東京化成製 試薬)2部加え、100℃2時間反応させ、その後、110−120℃で還流状態とし、そのまま7時間反応を行った。
反応終了後、メチルイソブチルケトン200部を加え、水洗を繰り返し、水層が中性になったことを確認した後、油層からロータリーエバポレーターを用いて減圧下、溶剤類を留去することで本発明の多価フェニレンエーテルノボラック樹脂(P−1)を179部を得た。(なお、原料であるポリフェニレンエーテル樹脂のGPCチャートではMn=2091、Mw=4215、Mz=7774であった。)Example 1
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 175 parts of polyphenylene ether resin (MX90-100, manufactured by Subic, Mn = 2066, Mw = 3553, Mz = 5951 on the GPC chart) while purging with nitrogen, p- Add 9.6 parts of xylylene glycol (reagent made by Tokyo Kasei), 300 parts of toluene (reagent made by Junsei Kagaku), 2 parts of paratoluenesulfonic acid monohydrate (reagent made by Tokyo Chemical Industry), and react at 100 ° C. for 2 hours. Then, it was made to reflux at 110-120 degreeC, and it reacted for 7 hours as it was.
After completion of the reaction, 200 parts of methyl isobutyl ketone was added, washing with water was repeated, and after confirming that the aqueous layer became neutral, the solvent was distilled off from the oil layer under reduced pressure using a rotary evaporator. 179 parts of a polyvalent phenylene ether novolak resin (P-1) was obtained. (In the GPC chart of the raw material polyphenylene ether resin, Mn = 2091, Mw = 4215, and Mz = 7774.)
(実施例2)
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながらポリフェニレンエーテル樹脂(サビック製 MX90-100)75部、p−キシリレングリコール(東京化成製 試薬)5部、トルエン(純正化学製 試薬)130部、パラトルエンスルホン酸・一水和物(東京化成製 試薬)1部加え、100℃2時間反応させ、その後、110−120℃で還流状態とし、そのまま10時間反応を行った。
反応終了後、メチルイソブチルケトン100部を加え、水洗を繰り返し、水層が中性になったことを確認した後、油層からロータリーエバポレーターを用いて減圧下、溶剤類を徐々に除去し、水の流出がなくなったことを確認し、メチルイソブチルケントンを追加し、樹脂濃度50%に調整した。これにより本発明の多価フェニレンエーテルノボラック樹脂ワニス(V−1)を143部を得た。GPCのチャートでは、Mn=2111、Mw=4345、 Mz=7932であった。(Example 2)
In a flask equipped with a stirrer, reflux condenser, and stirrer, 75 parts of polyphenylene ether resin (MX90-100 made by Subic), 5 parts of p-xylylene glycol (reagent made by Tokyo Chemical Industry), toluene (genuine) while purging with nitrogen Chemical reagent) 130 parts, p-toluenesulfonic acid monohydrate (Tokyo Kasei reagent) 1 part was added, reacted at 100 ° C. for 2 hours, then brought to reflux at 110-120 ° C. and reacted for 10 hours. It was.
After completion of the reaction, 100 parts of methyl isobutyl ketone was added, washing with water was repeated, and after confirming that the aqueous layer became neutral, the solvents were gradually removed from the oil layer under reduced pressure using a rotary evaporator. After confirming that the outflow disappeared, methyl isobutylkenton was added to adjust the resin concentration to 50%. As a result, 143 parts of the polyvalent phenylene ether novolak resin varnish (V-1) of the present invention was obtained. In the GPC chart, Mn = 2111, Mw = 4345, and Mz = 7932.
(実施例3)
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながらポリフェニレンエーテル樹脂(サビック製 MX90-100)87.5部、p−キシリレングリコール(東京化成製 試薬)4.8部、メチルイソブチルケトン(純正化学製 試薬)138部、パラトルエンスルホン酸・一水和物(東京化成製 試薬)1部加え、100℃2時間反応させ、その後、110−120℃で還流状態とし、そのまま7時間反応を行った。
反応終了後、メチルイソブチルケトン100部を加え、水洗を繰り返し、水層が中性になったことを確認した後、油層からロータリーエバポレーターを用いて減圧下、溶剤類を徐々に除去し、水の流出がなくなったことを確認し、メチルイソブチルケントンを追加し、樹脂濃度60%に調整した。
得られた本発明の多価フェニレンエーテルノボラック樹脂ワニス(V−2)を50部、フェノールビフェニレンノボラック(日本化薬製 KAYAHARD GPH-65)70部加え、溶解した後、ロータリーエバポレーターで減圧下、溶剤類を留去し、本発明の多価フェニレンエーテルノボラック樹脂が30%含有された、硬化剤組成物(H-1)を得た。軟化点は121℃であった、(Example 3)
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen while 87.5 parts of a polyphenylene ether resin (MX90-100, manufactured by Savic) and 4.8 parts of p-xylylene glycol (a reagent manufactured by Tokyo Chemical Industry). , 138 parts of methyl isobutyl ketone (reagent manufactured by Junsei Kagaku), 1 part of paratoluenesulfonic acid monohydrate (reagent manufactured by Tokyo Kasei Co., Ltd.), reacted at 100 ° C. for 2 hours, and then brought to reflux at 110-120 ° C. The reaction was carried out for 7 hours.
After completion of the reaction, 100 parts of methyl isobutyl ketone was added, washing with water was repeated, and after confirming that the aqueous layer became neutral, the solvents were gradually removed from the oil layer under reduced pressure using a rotary evaporator. After confirming that the outflow disappeared, methylisobutylkenton was added to adjust the resin concentration to 60%.
50 parts of the obtained polyphenylene ether novolak resin varnish (V-2) of the present invention and 70 parts of phenol biphenylene novolak (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.) were added and dissolved, and then the solvent was removed under reduced pressure using a rotary evaporator. Then, a curing agent composition (H-1) containing 30% of the polyvalent phenylene ether novolak resin of the present invention was obtained. The softening point was 121 ° C.,
(実施例4)
実施例3中、フェノールビフェニレンノボラック(日本化薬製 KAYAHARD GPH-65)70部を30部に変えた以外は同様に操作を行い、本発明の硬化剤組成物(H-2)を得た。
(実施例5)
実施例3中、フェノールビフェニレンノボラック(日本化薬製 KAYAHARD GPH-65)70部を20部に変えた以外は同様に操作を行い、本発明の多価フェニレンエーテルノボラック樹脂が60%含有された、硬化剤組成物(H-3)を得た。軟化点は130℃であった。Example 4
In Example 3, the same operation was performed except that 70 parts of phenol biphenylene novolak (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.) was changed to 30 parts, to obtain a curing agent composition (H-2) of the present invention.
(Example 5)
In Example 3, the same operation was performed except that 70 parts of phenol biphenylene novolak (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.) was changed to 20 parts, and 60% of the polyvalent phenylene ether novolac resin of the present invention was contained. A curing agent composition (H-3) was obtained. The softening point was 130 ° C.
(実施例6)
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながらポリフェニレンエーテル樹脂(サビック製 SA120-100 、GPC測定においてMn=2960、 Mw=6863、Mz=11851)100部、p−キシリレングリコール(東京化成製 試薬)10部、トルエン(純正化学製 試薬)140部、パラトルエンスルホン酸・一水和物(東京化成製 試薬)2.0部加え、100℃2時間反応させ、その後、110−120℃で還流状態とし、そのまま7時間反応を行った。
反応終了後、メチルエチルケトン100部を加え、メタノール1000部を入れた容器に徐々に滴下し、再沈殿を行った。得られた樹脂粉末を濾過後、メタノール:水=1:1 100部で洗浄した後、水100部で5回洗浄を行った。これにより、本発明の多価フェニレンエーテルノボラック樹脂(P−3)を89部を得た。GPCのチャートではMn=3683、Mw=7356、Mz=11860であった。また、得られた(P-3)30部に対し、KAYAHARD GPH-65を20部、トルエン50部を使用し、混合した後、ロータリーエバポレーターで減圧下、溶剤類を留去し、硬化剤組成物(H-4)を得た。(Example 6)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 100 parts of polyphenylene ether resin (SA120-100 manufactured by Subic, Mn = 2960, Mw = 6863, Mz = 11851 in GPC measurement) while purging with nitrogen, p- Add 10 parts of xylylene glycol (reagent made by Tokyo Kasei), 140 parts of toluene (reagent made by Junsei Kagaku), 2.0 parts of paratoluenesulfonic acid monohydrate (reagent made by Tokyo Chemical Industry), and react at 100 ° C. for 2 hours. Then, it was made to reflux at 110-120 degreeC, and it reacted for 7 hours as it was.
After completion of the reaction, 100 parts of methyl ethyl ketone was added, and the mixture was gradually added dropwise to a container containing 1000 parts of methanol, and reprecipitation was performed. The obtained resin powder was filtered, washed with 100 parts of methanol: water = 1: 1, and then washed 5 times with 100 parts of water. As a result, 89 parts of the polyvalent phenylene ether novolak resin (P-3) of the present invention were obtained. In the GPC chart, Mn = 3683, Mw = 7356, and Mz = 1860. Also, 20 parts of KAYAHARD GPH-65 and 50 parts of toluene were mixed with 30 parts of the obtained (P-3), and after mixing, the solvents were distilled off under reduced pressure using a rotary evaporator. A product (H-4) was obtained.
(比較例1)
ポリフェニレンエーテル樹脂(サビック製 MX90-100)を30部、フェノールビフェニレンノボラック(日本化薬製 KAYAHARD GPH-65)70部加え、メチルイソブチルケトンに溶解した後、ロータリーエバポレーターで減圧下、溶剤類を留去し、比較用の硬化剤組成物(H’-1)を得た。
(比較例2)
ポリフェニレンエーテル樹脂(サビック製 MX90-100)を30部、フェノールビフェニレンノボラック(日本化薬製 KAYAHARD GPH-65)20部加え、メチルイソブチルケトンに溶解した後、ロータリーエバポレーターで減圧下、溶剤類を留去し、比較用の硬化剤組成物(H’-2)を得た。(Comparative Example 1)
Add 30 parts of polyphenylene ether resin (MX90-100 from Savic) and 70 parts of phenol biphenylene novolak (KAYAHARD GPH-65 from Nippon Kayaku), dissolve in methyl isobutyl ketone, and then remove the solvents under reduced pressure using a rotary evaporator. Then, a comparative curing agent composition (H′-1) was obtained.
(Comparative Example 2)
Add 30 parts of polyphenylene ether resin (MX90-100 from Savic) and 20 parts of phenol biphenylene novolak (KAYAHARD GPH-65 from Nippon Kayaku), dissolve in methyl isobutyl ketone, and then remove the solvents under reduced pressure using a rotary evaporator. Then, a comparative curing agent composition (H′-2) was obtained.
実施例7〜8及び比較例3
<誘電率・誘電正接試験>
前記で得られた硬化剤組成物及びエポキシ樹脂等を表1の割合(重量部)で配合し、ミキシングロールを用いて均一に混合・混練し、封止用エポキシ樹脂組成物を得た。このエポキシ樹脂組成物をミキサーにて粉砕し、更にタブレットマシーンにてタブレット化した。このタブレット化されたエポキシ樹脂組成物をトランスファー成型(175℃×60秒)し、更に脱型後160℃×2時間+180℃×6時間の条件で硬化、評価用試験片を得た。
なお、硬化物の物性は以下の要領で測定した。
・誘電率・誘電正接:空洞共振器法
使用機器 関東電気応用開発 空洞共振器1GHz
リファレンス テフロン(登録商標)Examples 7 to 8 and Comparative Example 3
<Dielectric constant and dielectric loss tangent test>
The curing agent composition and epoxy resin obtained above were blended in the proportions (parts by weight) shown in Table 1, and mixed and kneaded uniformly using a mixing roll to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation.
In addition, the physical property of hardened | cured material was measured in the following ways.
・ Dielectric constant / dielectric loss tangent: Cavity resonator method Equipment used Kanto Electric Application Development Cavity resonator 1 GHz
Reference Teflon (registered trademark)
実施例9及び比較例4
<誘電特性試験・耐熱性試験>
前記で得られた硬化剤組成物及びエポキシ樹脂等を表2の割合(重量部)で配合し、ミキシングロールを用いて均一に混合・混練し、封止用エポキシ樹脂組成物を得た。このエポキシ樹脂組成物をミキサーにて粉砕し、更にタブレットマシーンにてタブレット化した。このタブレット化されたエポキシ樹脂組成物をトランスファー成型(175℃×60秒)し、更に脱型後160℃×2時間+180℃×6時間の条件で硬化、評価用試験片を得た。
なお、硬化物の物性は以下の要領で測定した。
・誘電率・誘電正接:空洞共振器法
使用機器 関東電気応用開発 空洞共振器1GHz
リファレンス テフロン(登録商標)
・耐熱性(TMA):JIS K 7244に準拠して測定した。Example 9 and Comparative Example 4
<Dielectric property test and heat resistance test>
The curing agent composition and the epoxy resin obtained as described above were blended in the proportions (parts by weight) shown in Table 2, and mixed and kneaded uniformly using a mixing roll to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation.
In addition, the physical property of hardened | cured material was measured in the following ways.
・ Dielectric constant / dielectric loss tangent: Cavity resonator method Equipment used Kanto Electric Application Development Cavity resonator 1 GHz
Reference Teflon (registered trademark)
Heat resistance (TMA): Measured according to JIS K 7244.
実施例10及び比較例5
<耐熱性試験・誘電特性試験>
前記で得られた硬化剤組成物及びエポキシ樹脂等を表3の割合(重量部)で配合し、ミキシングロールを用いて均一に混合・混練し、封止用エポキシ樹脂組成物を得た。このエポキシ樹脂組成物をミキサーにて粉砕し、更にタブレットマシーンにてタブレット化した。このタブレット化されたエポキシ樹脂組成物をトランスファー成型(175℃×60秒)し、更に脱型後160℃×2時間+180℃×6時間の条件で硬化、評価用試験片を得た。
なお、硬化物の物性は以下の要領で測定した。
・誘電率・誘電正接:空洞共振器法
使用機器 関東電気応用開発 空洞共振器1GHz
リファレンス テフロン(登録商標)
・耐熱性(DMA)
動的粘弾性測定器:TA−instruments、DMA−2980
測定温度範囲:−30〜280℃
温速度:2℃/分
試験片サイズ:5mm×50mmに切り出した物を使用した(厚みは約800μm)
Tg:Tan−δのピーク点をTgとした
・耐熱性(TMA):JIS K 7244に準拠して測定した。Example 10 and Comparative Example 5
<Heat resistance test / dielectric property test>
The curing agent composition and the epoxy resin obtained above were blended in the proportions (parts by weight) shown in Table 3, and mixed and kneaded uniformly using a mixing roll to obtain an epoxy resin composition for sealing. This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C. × 60 seconds), and after demolding, cured under the conditions of 160 ° C. × 2 hours + 180 ° C. × 6 hours to obtain a test piece for evaluation.
In addition, the physical property of hardened | cured material was measured in the following ways.
・ Dielectric constant / dielectric loss tangent: Cavity resonator method Equipment used Kanto Electric Application Development Cavity resonator 1 GHz
Reference Teflon (registered trademark)
・ Heat resistance (DMA)
Dynamic viscoelasticity measuring device: TA-instruments, DMA-2980
Measurement temperature range: -30 to 280 ° C
Temperature rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out (thickness is about 800 μm)
Tg: Tan-δ peak point was Tg. Heat resistance (TMA): Measured in accordance with JIS K 7244.
以上の結果から、本発明の硬化性樹脂組成物は、硬化剤(組成物)として、類似構造を有するH’-1、H’-2を使用したものと比較し、耐熱性にも優れることが明らかであり、また他の硬化剤を使用したものと比較して誘電率・誘電正接も良く、優れた誘電特性を有することが確認された。 From the above results, the curable resin composition of the present invention is excellent in heat resistance as compared with those using H'-1 and H'-2 having a similar structure as a curing agent (composition). It was clear that the dielectric constant and dielectric loss tangent were good as compared with those using other curing agents, and it was confirmed that they have excellent dielectric properties.
本発明を特定の態様を参照して詳細に説明したが、本発明の精神と範囲を離れることなく様々な変更および修正が可能であることは、当業者にとって明らかである。
なお、本出願は、2012年11月6日付で出願された日本国特許出願(特願2012−244309)に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
In addition, this application is based on the Japan patent application (Japanese Patent Application No. 2012-244309) for which it applied on November 6, 2012, The whole is used by reference. Also, all references cited herein are incorporated as a whole.
本発明のポリフェニレンエーテルノボラック樹脂は、エポキシ樹脂の硬化剤等として有用であり、該ポリフェニレンエーテルノボラック樹脂を硬化剤として含むエポキシ樹脂組成物は、電気電子部品用絶縁材料及び積層板(プリント配線板、ビルドアップ基板など)やCFRPを始めとする各種複合材料、接着剤、塗料等に有用である。 The polyphenylene ether novolak resin of the present invention is useful as a curing agent for an epoxy resin, and the epoxy resin composition containing the polyphenylene ether novolak resin as a curing agent includes an insulating material for electrical and electronic parts and a laminate (printed wiring board, It is useful for various composite materials such as build-up substrates) and CFRP, adhesives, paints and the like.
Claims (5)
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JP2012244309 | 2012-11-06 | ||
PCT/JP2013/079920 WO2014073536A1 (en) | 2012-11-06 | 2013-11-05 | Polyvalent phenylene ether novolac resin, epoxy resin composition, and cured product thereof |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04183707A (en) * | 1990-11-19 | 1992-06-30 | Mitsubishi Petrochem Co Ltd | Production of polyphenylene ether crosslinked molded product |
JP2006274241A (en) * | 2005-03-25 | 2006-10-12 | Korea Research Inst Of Chemical Technology | Aromatic polyether resin crosslinked with amic acid or imide side chain group |
JP2011074123A (en) * | 2009-09-29 | 2011-04-14 | Panasonic Electric Works Co Ltd | Resin composition, resin varnish, prepreg, metal-clad laminate, and printed wiring board |
JP2011084626A (en) * | 2009-10-14 | 2011-04-28 | Jsr Corp | Resin composition and its application |
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JP4736254B2 (en) | 2001-06-28 | 2011-07-27 | 三菱瓦斯化学株式会社 | Bifunctional phenylene ether oligomer and its production method |
US7595362B2 (en) * | 2004-01-30 | 2009-09-29 | Nippon Steel Chemical Co., Ltd. | Curable resin composition |
JP5311717B2 (en) | 2005-03-14 | 2013-10-09 | 旭化成ケミカルズ株式会社 | Process for producing polyfunctional polyphenylene ether |
EP1988112A4 (en) * | 2006-02-21 | 2012-02-01 | Asahi Kasei Chemicals Corp | Process for producing low-molecular polyphenylene ether |
JP5104507B2 (en) * | 2007-04-26 | 2012-12-19 | 日立化成工業株式会社 | Process for producing resin varnish containing thermosetting resin of semi-IPN type composite, and resin varnish for printed wiring board, prepreg and metal-clad laminate using the same |
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- 2013-11-05 WO PCT/JP2013/079920 patent/WO2014073536A1/en active Application Filing
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04183707A (en) * | 1990-11-19 | 1992-06-30 | Mitsubishi Petrochem Co Ltd | Production of polyphenylene ether crosslinked molded product |
JP2006274241A (en) * | 2005-03-25 | 2006-10-12 | Korea Research Inst Of Chemical Technology | Aromatic polyether resin crosslinked with amic acid or imide side chain group |
JP2011074123A (en) * | 2009-09-29 | 2011-04-14 | Panasonic Electric Works Co Ltd | Resin composition, resin varnish, prepreg, metal-clad laminate, and printed wiring board |
JP2011084626A (en) * | 2009-10-14 | 2011-04-28 | Jsr Corp | Resin composition and its application |
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TW201431901A (en) | 2014-08-16 |
WO2014073536A1 (en) | 2014-05-15 |
CN104781307A (en) | 2015-07-15 |
KR20150082181A (en) | 2015-07-15 |
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